醛基功能化金属-有机骨架材料的构筑及其对巯基氨基酸的识别研究

Selective recognition and sensing of mercaptoamino-acid is an important subject of biochemistry and clinical medical research, and has important theoretical value and application significance for exploring and understanding cell metabolism and redox essence in the life system. Porous metal–organic frameworks (MOFs) represent a new class of inorganic–organic supramolecular hybrid materials comprising ordered net-works formed from organic electron donor linkers and metal cations. Their tunable pore size and characteristic functionality that are similar to active sites in proteins suggests they may act as bright promising host matrices for molecular recognition. In this project, through incorporating acridine compounds, which exhibits good biological activities and medicinal physiological activity and can be used for pharmaceutical industry as strong fluorescent matrix unit, cleverly grafting aldehyde groups, new fluorescent MOFs will be produced to recognize some mercaptoamino-acid with high selectivity by the specific interaction between aldehyde groups and sulfhydryl groups, channel restrictions and good matching in space and energy. And realize the ratiometric fluorescent response to mercaptoamino-acid and chiral recognition research by choosing the rare earth ions as the nodes or chiral aldehyde group ligands, solve a series of scientific problems, such as the regulation of the channel size and stereoscopic effect and reasonable layout of recognition function sites and so on. On the basis of high selective recognition, optimal MOFs can be scaled down to the nanoregime to form nanoscale metal-organic frameworks (NMOFs) to be swallowed by the cells to be implicated biological imaging of mercaptoamino-acid in the living cells. This project not only provides a new way for preparing functionalized MOFs, but also provides innovative research ideas for the construction of new biological molecular devices.

对巯基氨基酸的选择性识别是生物化学和临床医学研究的重要课题，对探索和理解生命体系中细胞新陈代谢和氧化还原的本质具有重要的理论价值和实际应用意义。本项目将以高灵敏、高选择性地检测巯基氨基酸为研究突破口，通过选择具有良好生物活性和生理活性，广泛用于制药行业的吖啶类化合物为荧光母体衍生羧酸配位位点，将醛基基团巧妙引入，并与合适的金属离子配位，构筑具有孔道结构的金属-有机骨架材料，通过醛基与巯基特异性的反应协同骨架结构孔道尺寸的筛选以及在空间和能量上良好的匹配，实现对特定巯基氨基酸的高选择性识别；通过引入稀土离子构筑比率荧光探针来提高识别过程的灵敏度；同时构筑含手性醛基的MOFs，进行巯基氨基酸手性识别的探索；最后，在高选择性识别的基础上，将最优的MOFs通过微波法制成纳米尺寸的NMOFs，进行细胞成像应用。本项目不仅为制备功能化MOFs提供了崭新的途径，也为构建新型生物分子器件提供创新研究思路。

当今世界，人类面临的最大问题就是环境污染严重和能源消耗过大。其中，挥发性有机蒸汽（VOCs）、有毒金属离子、pH及硝基爆炸物等是社会重要的污染源，因其对环境和人类的危害，实现对其灵敏的分析检测具有十分重要的研究意义和社会价值。化石燃料作为一种传统的能源，被人类大量利用，其燃烧产生的气体对大气环境造成了严重的污染，而且化石燃料作为不可再生能源，它的储量是有限的。因此寻找替代化石燃料的方法促使人们越来越关注利用低碳或碳中和能源。本研究着眼于金属-有机骨架结构（MOFs）特殊的结构特点——易衍生荧光功能和引入响应中心，可以从分子设计层面方便地调节材料的识别位点分布和发射光谱的范围，制备具备高选择性、快速响应、高灵敏度的MOFs材料，研究其在氨基酸生物分子识别、污染物检测和降解以及光解水制氢等三方面的应用和其构效关系的探讨，这一系列的研究成果为发展和构建安全、和谐的安全检测、保护体系具有重要的指导意义。在本项目支持下，在J. Mater. Chem. A（2篇,被选为当期封面文章）、Inorg. Chem.（2篇）、Chem. Eur. J.（1篇）、Dyes Pigments（1篇）、New J. Chem.（1篇）和RSC Adv.（1篇）等学术期刊发表标注论文9篇，均为影响因子大于3.0的SCI论文，申请专利1项。.